US3598879A - Alkyl transfer of alkyl aromatics with group i-a,ii-a,iv,or rare earth metals on boria alumina - Google Patents
Alkyl transfer of alkyl aromatics with group i-a,ii-a,iv,or rare earth metals on boria alumina Download PDFInfo
- Publication number
- US3598879A US3598879A US785232A US3598879DA US3598879A US 3598879 A US3598879 A US 3598879A US 785232 A US785232 A US 785232A US 3598879D A US3598879D A US 3598879DA US 3598879 A US3598879 A US 3598879A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- group
- toluene
- catalyst
- xylenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- a process for the alkyl transfer of alkyl aromatics including contacting an alkyl aromatic feed material, such as toluene, with a catalyst comprising a metal of Group I-A, such as potassium, rubidium, cesium, etc., Group II-A, such as calcium, magnesium, strontium, etc., Group IV, such as tin, lead, titanium, zirconium, etc., or rare earth metals, such as cerium, thorium, etc., of the Periodic System or mixtures thereof and boria deposited on an alumina base at a temperature of about 800 to 1100 F., a pressure of about 0 to 2000 p.s.i.g., and a liquid hourly space velocity of about 0.1 to l0,'and in the presence of hydrogen introduced at a rate of about 1 to 10 moles hydrogen per mole of hydrocarbon feed.
- a catalyst comprising a metal of Group I-A, such as potassium, rubidium, cesium, etc., Group II-A,
- Promoters selected from Group I, Group II, Group IV, and the rare earth metals of the Periodic System may be added to the catalyst.
- Deactivated catalyst may be periodically rejuvenated by discontinuing the introduction of aromatic feed material and purging with hydrogen and the catalyst can be reactivated by calcination in an atmosphere such as air.
- the alkyl transfer product may be distilled to separate benzene, toluene and xylenes, the toluene may be recycled to the alkyl transfer step, the xylenes may be crystallized to separate para-xylene from the remaining xylenes, the mother liquor from the crystallization step may thereafter be isomerized to readjust the para-xylene content and the product of the isomerization may be recycled to the crystallization zone.
- the present invention relates to a process for the catalytic conversion of hydrocarbons and, more particularly, to a process for the catalytic alkyl transfer of alkyl aromatics.
- Aromatic hydrocarbons such as benzene, naphthalene, and their alkyl derivatives are important building blocks in the chemical and petrochemical industries.
- benzene and its derivatives have numerous uses; cyclohexane is utilized in nylon production; naphthalene is utilized in the production of phthalic anhydride for alkyd resins, etc.; para-xylene can be used for the production of terephthalic acid which, in turn, is utilized in the production of synthetic resins, such as Dacron, Mylar, etc., etc.
- coal tar oils obtained by the pyrolysis of coal to produce coke.
- Such coal tar oils contain principally benzene, toluene, naphthalene, methylnaphthalene and para-xylene.
- Benzene may be produced from such oils by direct separation, such as distillation techniques, the para-xylene may be separated by crystallization, and the naphthalene fractions by direct separation techniques. Further alkyl derivatives of benzene and naphthalene can be converted to increased volumes of benzene and naphthalene by hydrodealkylation.
- An alkyl transfer reaction is a process wherein alkyl groups are caused to be transferred from the nuclear carbon atoms of one aromatic molecule to the nuclear carbon atoms of another aromatic molecule.
- an aromatic hydrocarbon molecule containing one nuclear alkyl substituent such as toluene
- an aromatic hydrocarbon molecule containing one nuclear alkyl substituent such as toluene
- aromatic hydrocarbon molecules with two nuclear alkyl substituents namely xylenes.
- product ratios may be shifted by transalkylation of xylene and benzene to toluene.
- Such an alkyl transfer reaction has distinct advantages: methane is not produced, but instead, valuable aromatic hydrocarbons are produced in addition to the desired aromatic hydrocarbon. As a result, there is very little loss of product in alkyl transfer as opposed to hydrodealkylation.
- Alkyl transfer may be carried out thermally.
- thermal alkyl transfer results in demethylation due to cracking and hydrogenation, ultimately resulting in low yields of desired aromatics.
- catalytic alkyl transfer has not been highly successful since it requires an active, rugged, acidic catalyst.
- Typical catalysts are solid oxides, such as silica-alumina, silica-magnesium, etc. These materials, however, are not active enough to promote disproportionation at high conversion rates.
- carbon deposition on the catalyst and its effect on catalyst activity with time is a severe problem.
- a further object of the present invention is to provide an improved process for the catalytic disproportionation of alkyl aromatics utilizing a Group I-A, II-A, IV or rare earth metal and boria on an alumina base.
- a further object of the present invention is to provide an improved process for the disproportionation of alkyl aromatics utilizing critical conditions of temperature and pressure which produce maximum disproportionation and conversion of one aromatic to another.
- Still another object of the present invention is to provide an improved process for the conversion of toluene to benzene and xylenes and conversion of meta-, and ortho-xylenes to additional para-xylene.
- alkyl transfer of alkyl aromatics comprises contacting an alkyl aromatic feed material with a catalyst comprising a metal of Group I-A, Group II-A, Group IV, a rare earth metal or mixtures thereof and boria deposited on an alumina base. Further improvements of the process are obtained by maintaining the temperature between about 800 and 1100 F. and the pressure between about and 2000 p.s.i.g. Where toluene is the feed, additional para-xylene is produced by isomerizing orthoand meta-xylenes.
- Alkyl aromatic feed materials for use in accordance with the present invention can be any alkyl aromatic having at least one transferable alkyl group.
- Primary materials are alkyl aromatics having from 7 to carbon atoms, mixtures of such alkyl aromatic hydrocarbons, or hydrocarbon fractions rich in such alkyl aromatic hydrocarbons.
- Such feeds include monoand di-aromatics, such as alkyl benzenes and alkyl naphthalenes.
- the alkyl group should contain no more than about 4 carbon atoms.
- a preferred feed in accordance with the present invention is toluene. Accordingly, disproportionation of toluene will be referred to hereinafter in the detailed description.
- the process of the present invention should be conducted at a temperature between about 800 and 1100 F., and preferably between 850 and 1000 F. It has been found in accordance with the present invention that below this temperature range substantially decreased conversion occurs due to hydrogenation. On the other hand, when operating above this temperature range, thermal demethylation occurs.
- the pressure utilized in accordance with the present invention has also been determined to be a critical factor. Accordingly, the process should be carried out between about 0 and 2000 p.s.i.g. and preferably, between 300 to 600 p.s.i.g. It has been found that below the desired pressure range, conversion is low and the aromaticity of the product is high. On the other hand, at higher pressures, conversion is high, but liquid recoveries are low due to hydrogenation and hydrocracking.
- a liquid hourly space velocity between about 0.1 and 10, and preferably between 0.25 and 1.0, should be utilized and a hydrogen-to-hydrocarbon mole ratio between about I and 10 to 1 and preferably 2 and 4 to 1 is desired.
- the catalyst employed in accordance with the present invention is a multi-faceted cure for many of the ills of catalytic disproportionation reactions.
- boria deposited on an alumina base is vastly superior to a silica-alumina base catalyst; the former consistently proving to be twice as active as the latter.
- the amount of boria deposited on the alumina may vary between about 5 and 25% by weight of the finished catalyst.
- the alumina is preferably a gamma alumina. Such gamma aluminas are very stable up to temperatures of about 1800 F.
- Boehmite may be prepared in a variety of Ways, one of the simplest being the addition of ammonium hydroxide to a water solution of aluminum chloride.
- the material originally precipitated is an amorphous alumina flock which rapidly grows to crystal size yielding crystalline Boehmite.
- Aging of Boehmite in ammonium hydroxide solution transforms the Boehmite first to the meta-stable Bayerite and finally to the highly stable Gibbsite.
- the Bayerite is preferred and may be in its betaor eta-form.
- the active metal added to the boria-alumina may be selected from Group I-A of the Periodic System, such as potassium, rubidium, cesium, etc., Group II-A of the Periodic System, such as calcium, magnesium, strontium, etc., a rare earth metal of the Periodic System, such as cerium, thorium, etc., a Group IV metal of the Periodic System, such as tin, lead, titanium, zirconium, etc., or mixtures of these, and particularly mixtures of a Group IV metal with one of the other groups mentioned.
- the active metals are preferably in their oxide form and are present in amounts of about 1 to 15% by weight based on the weight of the finished catalyst.
- the catalysts may be prepared by techniques well known in the art. For example, such preparation may include coprecipitation or impregnation techniques. One can employ extrudates or pellets for impregnation of powders followed by pelletization or extrusion to yield the finished catalyst. When employing impregnation techniques, the metals may be added to the base singly or in combination, utilizing water soluble salts such as borates, boric acid, halides, nitrates, sulfates, acetates, etc. Easily hydrolyzed salts can be kept in solution without decomposition by employing the appropriate inorganic acids. Well-known procedures for drying and calcination of the catalyst will also be employed. For example, vacuum drying at a temperature of about 250 F. and calcination in an oxidative, neutral or reductive atmosphere, utilizing a calcination temperature of about 800 to 1200 F. can be practiced.
- water soluble salts such as borates, boric acid, halides, n
- Table I illustrates the advantages of a tin-boria-alumina catalyst as compared with boria-alurnina alone for the disproportionation of toluene at 948 F., 800 p.s.i.g., a liquid hourly space velocity of 0.44 and a hydrogen-to-hydrocarbon ratio of 3/ 1.
- an integrated process for the production of benzene and para-xylene from toluene can be carried outwith resultant high yields of these two valuable products. This process is best described by reference to the drawing.
- toluene is introduced to the system through line 10, hydrogen is added through line 12 and these materials are passed over the catalyst of the present invention in the disproportionation reactor 14.
- the efiluent passing through line 16 is passed to a flash drum for the removal of hydrogen and any light gases produced. These materials are discharged through line 18. Since little or no demethanation occurs, the hydrogen is substantially pure and may be recycled to the disproportionation reaction without further treatment. However, in some instances, further purification of the hydrogen is necessary before recycle or reuse.
- the liquid product passes through line 20 to a first distillation unit 22. In distillation unit 22, benzene is recovered as an overhead through line 24. The bottoms product from distillation unit 22 passes through line 26 to a second distillation unit 28.
- distillation unit 28 toluene is removed as an overhead product and recycled to the disproportionation section through line 30.
- the bottoms product from distillation unit 28 is a mixture of xylenes which is discharged through line 32. This product may be withdrawn, as such, through line 34.
- the xylene product is passed through line 36 to crystallization unit 38.
- crystallization unit 38 para-xylene is selectively removed and withdrawn through line 40.
- the mother liquor from the crystallization section is passed through line 42 to an isomerization unit 44. Hydrogen is added through line 46.
- the equilibrium concentration of para-xylene is re-established and the material may then be recycled through line 48 to crystallization unit 38 for further para-xylene separation.
- the isomerization reaction should be carried out under more mild conditions than the disproportionation. Catalysts useful in the disproportionation reaction might also be used in the isomerization or conventional catalysts, such as platinum on silica-alumina, can be used.
- the isomerization may be carried out at temperatures of about 500 to 900 F., and preferably 550 to 650 F., pressures of 50 to 2000 p.s.i.g., and preferably 300 to 600 p.s.i.g., at a liquid hourly space velocity of 0.1 to 10, and utilizing a hydrogen-to-hydrocar-bon mole ratio between about 1 and 20 to l.
- the present invention is further exemplified by the following Table II.
- Table IV shows the results of using stoichiometric or greater amounts of a metal salt with boric acid to prepare the catalyst, thereby producing a metal borate. Accordingly, less than stoichiometric amounts of the metal should be used with the boria.
- alkyl transfer of alkyl aromatics as used herein is meant to include disproportionation and transalkylation.
- Disproportionation in turn, is meant to include conversion of two moles of a single aromatic, such as toluene, to one mole each of two different aromatics, such as xylenes and benzene.
- Transalkylation is meant to include conversion of one mole each of two different aromatics, such as xylenes and benzene, to one mole of a single different aromatic such as toluene.
- Table III shows the use of a catalyst, made in accordance with the present invention, to disproportionate xylene.
- fer defined above is also to be distinguished from isomerization where there is no transfer of alkyl groups from one molecule to another 'but simply a shifting of alkyl groups around the aromatic ring, such as isomerization of xylenes, or rupture of the ring or the alkyl side chain and rearrangement of split-off carbon atoms on the same molecule.
- the alkyl transfer is also to be distinguished from a hydrogen transfer reaction, such as the hydrogenation of aromatics, the dehydrogenation of cycloparaffins and like reactions.
- a process for the alkyl transfer of alkyl aromatics comprising, contacting an alkyl aromatic feed material with a catalyst consisting essentially of about 1 to 15% by weight of a metal of Groups I-A, II-A, IV and rare earth metals of the Periodic System and mixtures thereof and about 5 to 25% by weight of boria deposited on an alumina base, under conditions sufiicient to cause disproportionation of said alkyl aromatics.
- metal is a mixture of Group IV and a metal selected from the group consisting of Groups I-A, II-A and rare earth metals.
Abstract
A PROCESS FOR THE ALKYL TRANSFER OF ALKYL AROMATICS INCLUDING CONTACTING AN ALKYL AROMATIC FEED MATERIAL, SUCH AS TOLUENE, WITH A CATALYST COMPRISING A METAL OF GROUP I-A, SUCH AS POTASSIUM, RUBIDIUM, CESIUM, ETC., GROUP II-A, SUCH AS CALCIUM, MAGNESIUM, STRONTIUM, ETC., GROUP IV, SUCH AS TIN, LEAD, TITANIUM, ZIRCONIUM, ETC., OR RARE EARTH METALS, SUCH AS CERIUM, THORIUM, ETC., OF THE PERIODIC SYSTEM OR MIXTURES THEREOF AND BORIA DEPOSITED ON AN ALUMINA BASE AT A TEMPERATURE OF ABOUT 800 TO 1100*F., A PRESSURE OF ABOUT 0 TO 2000 P.S.I.G., AND A LIQUID HOURLY SPACE VELOCITY OF ABOUT 0.1 TO 10, AND IN THE PRESENCE OF HYDROGEN INTRODUCED AT A RATE OF ABOUT 1 TO 10 MOLES HYDROGEN PER MOLE OF HYDROCARBON FEED. PROMOTERS SELECTED FROM GROUP I, GROUP II, GROUP IV, AND THE RARE EARTH METALS OF THE PERIODIC SYSTEM MAY BE ADDED TO THE CATALYST. DEACTIVATED CATALYST MAY BE PERIODICALLY REJUVENATED BY DISCONTINUING THE INTRODUCTION OF AROMATIC FEED MATERIAL AND PURGING WITH HYDROGEN AND THE CATALYST CAN BE REACTIVATED BY CALCINATION IN AN ATMOSPHERE SUCH AS AIR. WHERE TOLUENE IS THE FEED, THE ALKYL TRANSFER PRODUCT MAY BE DISTILLED TO SEPARATE BENZENE, TOLUENE AND XYLENES, THE TOLUENE MAY BE RECYCLED TO THE ALKYL TRANSFER STEP, THE XYLENES MAY BE CRYSTALLIZED TO SEPARATE PARA-XYLENE FROM THE REMAINING XYLENES, THE MOTHER LIQUOR FROM THE CRYSTALLIZATION STEP MAY THEREAFTER BE ISOMERIZED TO READJUST THE PARA-XYLENE CONTENT AND THE PRODUCT OF THE ISOMERIZATION MAY BE RECYCLED TO THE CRYSTALLIZATION ZONE.
Description
United States Patent 3,598,879 ALKYL TRANSFER OF ALKYL AROMATICS WITH GROUP I-A, lI-A, IV, OR RARE EARTH METALS ON BORIA ALUMINA Ronald A. Kmecak and Stephen M. Kovach, Ashland, Ky., assignors to Ashland Oil, Inc., Houston, Tex. Filed Dec. 19, 1968, Ser. No. 785,232 Int. Cl. B01j 11/06; C07c 3/58, 15/08 US. Cl. 260-672 12 Claims ABSTRACT OF THE DISCLOSURE A process for the alkyl transfer of alkyl aromatics including contacting an alkyl aromatic feed material, such as toluene, with a catalyst comprising a metal of Group I-A, such as potassium, rubidium, cesium, etc., Group II-A, such as calcium, magnesium, strontium, etc., Group IV, such as tin, lead, titanium, zirconium, etc., or rare earth metals, such as cerium, thorium, etc., of the Periodic System or mixtures thereof and boria deposited on an alumina base at a temperature of about 800 to 1100 F., a pressure of about 0 to 2000 p.s.i.g., and a liquid hourly space velocity of about 0.1 to l0,'and in the presence of hydrogen introduced at a rate of about 1 to 10 moles hydrogen per mole of hydrocarbon feed. Promoters selected from Group I, Group II, Group IV, and the rare earth metals of the Periodic System may be added to the catalyst. Deactivated catalyst may be periodically rejuvenated by discontinuing the introduction of aromatic feed material and purging with hydrogen and the catalyst can be reactivated by calcination in an atmosphere such as air. Where toluene is the feed, the alkyl transfer product may be distilled to separate benzene, toluene and xylenes, the toluene may be recycled to the alkyl transfer step, the xylenes may be crystallized to separate para-xylene from the remaining xylenes, the mother liquor from the crystallization step may thereafter be isomerized to readjust the para-xylene content and the product of the isomerization may be recycled to the crystallization zone.
BACKGROUND OF THE INVENTION The present invention relates to a process for the catalytic conversion of hydrocarbons and, more particularly, to a process for the catalytic alkyl transfer of alkyl aromatics.
Aromatic hydrocarbons, such as benzene, naphthalene, and their alkyl derivatives are important building blocks in the chemical and petrochemical industries. For example, benzene and its derivatives have numerous uses; cyclohexane is utilized in nylon production; naphthalene is utilized in the production of phthalic anhydride for alkyd resins, etc.; para-xylene can be used for the production of terephthalic acid which, in turn, is utilized in the production of synthetic resins, such as Dacron, Mylar, etc., etc.
For many years, the primary source of such aromatic hydrocarbons has been coal tar oils obtained by the pyrolysis of coal to produce coke. Such coal tar oils contain principally benzene, toluene, naphthalene, methylnaphthalene and para-xylene. Benzene may be produced from such oils by direct separation, such as distillation techniques, the para-xylene may be separated by crystallization, and the naphthalene fractions by direct separation techniques. Further alkyl derivatives of benzene and naphthalene can be converted to increased volumes of benzene and naphthalene by hydrodealkylation.
More recently, however, the petroleum industry has become a leading source of these aromatic hydrocarbons. The reason for this has been the availability of the catalytic reforming process in which naphthene hydrocarbons Patented Aug. 10, 1971 "Ice are dehydrogenated to produce a reformate rich in aromatics and more eflicient processes for separating the aromatics from the reformate.
Some years ago, there was a high demand for toluene which was used in the production of TNT. This led to the building of substantial facilities for its production. However, the advent of nuclear and fusion weaponry and the use of diesel oil-ammonium nitrate explosives has left toluene in substantial over-supply, since the only major uses of toluene are as a solvent, the production of toluene diisocyanates and the production of benzene. This has resulted in extensive efforts to develop methods for converting toluene to benzene. One method of converting toluene to benzene is by the previously mentioned hydrodealkylation.
Dealkylation has the primary disadvantage that methane is a major product. Volume yields of benzene are therefore low and carbon deposition on the catalyst is high. The large amounts of methane, while useful as a fuel, require expensive techniques for the removal of the methane from the circulating hydrogen stream utilized in the hydrodealkylation. In addition, large quantities of hydrogen are consumed in the dealkylation process and hydrogen is often in short supply and expensive to produce. Finally, where catalysts are used in the process, carbon laydown on the catalyst is a serious problem.
A more profitable reaction for changing alkyl aromatics to other aromatic products is an alkyl transfer reaction. An alkyl transfer reaction is a process wherein alkyl groups are caused to be transferred from the nuclear carbon atoms of one aromatic molecule to the nuclear carbon atoms of another aromatic molecule. By way of example, an aromatic hydrocarbon molecule containing one nuclear alkyl substituent, such as toluene, may be treated by disproportionation to produce an aromatic hydrocarbon with no alkyl substituents, namely, benzene, and aromatic hydrocarbon molecules with two nuclear alkyl substituents, namely xylenes. Similarly, product ratios may be shifted by transalkylation of xylene and benzene to toluene. Such an alkyl transfer reaction has distinct advantages: methane is not produced, but instead, valuable aromatic hydrocarbons are produced in addition to the desired aromatic hydrocarbon. As a result, there is very little loss of product in alkyl transfer as opposed to hydrodealkylation.
Alkyl transfer may be carried out thermally. However, thermal alkyl transfer results in demethylation due to cracking and hydrogenation, ultimately resulting in low yields of desired aromatics. On the other hand, catalytic alkyl transfer has not been highly successful since it requires an active, rugged, acidic catalyst. Typical catalysts are solid oxides, such as silica-alumina, silica-magnesium, etc. These materials, however, are not active enough to promote disproportionation at high conversion rates. In addition, as is the case in hydrodealkylation, carbon deposition on the catalyst and its effect on catalyst activity with time is a severe problem.
It is therefore an object of the present invention to provide an improved process for the conversion of alkyl aromatics. Another object of the present invention is to provide an improved process for the alkyl transfer of alkyl aromatics. Yet another object of the present invention is to provide an improved process for the disproportionation of toluene to produce benzene and xylenes. Another and further object of the present invention is to provide an improved process for the disproportionation of alkyl aromatics which utilizes a novel catalyst system. Another object of the present invention is to provide an improved process for the disproportionation of alkyl aromatics with a catalyst system resistant to carbon laydown. A further object of the present invention is to provide an improved process for the catalytic disproportionation of alkyl aromatics utilizing a Group I-A, II-A, IV or rare earth metal and boria on an alumina base. A further object of the present invention is to provide an improved process for the disproportionation of alkyl aromatics utilizing critical conditions of temperature and pressure which produce maximum disproportionation and conversion of one aromatic to another. Still another object of the present invention is to provide an improved process for the conversion of toluene to benzene and xylenes and conversion of meta-, and ortho-xylenes to additional para-xylene. These and other objects and advantages of the present invention will be apparent from the following detailed description.
SUMMARY OF THE INVENTION Briefly, in accordance with the present invention, alkyl transfer of alkyl aromatics comprises contacting an alkyl aromatic feed material with a catalyst comprising a metal of Group I-A, Group II-A, Group IV, a rare earth metal or mixtures thereof and boria deposited on an alumina base. Further improvements of the process are obtained by maintaining the temperature between about 800 and 1100 F. and the pressure between about and 2000 p.s.i.g. Where toluene is the feed, additional para-xylene is produced by isomerizing orthoand meta-xylenes.
BRIEF DESCRIPTION OF THE DRAWING The drawing shows a flow diagram of a process system in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION Alkyl aromatic feed materials for use in accordance with the present invention can be any alkyl aromatic having at least one transferable alkyl group. Primary materials are alkyl aromatics having from 7 to carbon atoms, mixtures of such alkyl aromatic hydrocarbons, or hydrocarbon fractions rich in such alkyl aromatic hydrocarbons. Such feeds include monoand di-aromatics, such as alkyl benzenes and alkyl naphthalenes. Preferably, the alkyl group should contain no more than about 4 carbon atoms. A preferred feed in accordance with the present invention is toluene. Accordingly, disproportionation of toluene will be referred to hereinafter in the detailed description.
The process of the present invention should be conducted at a temperature between about 800 and 1100 F., and preferably between 850 and 1000 F. It has been found in accordance with the present invention that below this temperature range substantially decreased conversion occurs due to hydrogenation. On the other hand, when operating above this temperature range, thermal demethylation occurs. The pressure utilized in accordance with the present invention has also been determined to be a critical factor. Accordingly, the process should be carried out between about 0 and 2000 p.s.i.g. and preferably, between 300 to 600 p.s.i.g. It has been found that below the desired pressure range, conversion is low and the aromaticity of the product is high. On the other hand, at higher pressures, conversion is high, but liquid recoveries are low due to hydrogenation and hydrocracking. A liquid hourly space velocity between about 0.1 and 10, and preferably between 0.25 and 1.0, should be utilized and a hydrogen-to-hydrocarbon mole ratio between about I and 10 to 1 and preferably 2 and 4 to 1 is desired.
The high severity conditions required to obtain disproportionation of alkyl aromatics, particularly the disproportionation of toluene, has been found to lead to catalyst deactivation due to selective adsorption and condensation of aromatics on the catalyst surface and carbon laydown on the catalyst. It was found that the condensation and adsorption of aromatics on the catalyst is a temporary poison and that this condition can be alleviated by utilizing high hydrogen partial pressures. In addition, this temporary deactivation of the catalyst can be overcome to completely rejuvenate the catalyst to near virgin activity by.hydrogen-p-urging of the catalyst in the absence of aromatic hydrocarbon feed. While coke or carbon deposition on the catalyst is a permanent poison, it has been found, in accordance with the present invention, that carbon laydown can be decreased by utilizing the catalysts of the present invention. Further, it was found that when these catalysts become deactivated by carbon laydown, they can be restored to near virgin activity by regeneration in air.
The catalyst employed in accordance with the present invention is a multi-faceted cure for many of the ills of catalytic disproportionation reactions. First, it has been found that boria deposited on an alumina base is vastly superior to a silica-alumina base catalyst; the former consistently proving to be twice as active as the latter. The amount of boria deposited on the alumina may vary between about 5 and 25% by weight of the finished catalyst. The alumina is preferably a gamma alumina. Such gamma aluminas are very stable up to temperatures of about 1800 F. One such alumina, Boehmite, may be prepared in a variety of Ways, one of the simplest being the addition of ammonium hydroxide to a water solution of aluminum chloride. The material originally precipitated is an amorphous alumina flock which rapidly grows to crystal size yielding crystalline Boehmite. Aging of Boehmite in ammonium hydroxide solution transforms the Boehmite first to the meta-stable Bayerite and finally to the highly stable Gibbsite. The Bayerite is preferred and may be in its betaor eta-form.
The active metal added to the boria-alumina may be selected from Group I-A of the Periodic System, such as potassium, rubidium, cesium, etc., Group II-A of the Periodic System, such as calcium, magnesium, strontium, etc., a rare earth metal of the Periodic System, such as cerium, thorium, etc., a Group IV metal of the Periodic System, such as tin, lead, titanium, zirconium, etc., or mixtures of these, and particularly mixtures of a Group IV metal with one of the other groups mentioned. The active metals are preferably in their oxide form and are present in amounts of about 1 to 15% by weight based on the weight of the finished catalyst.
The catalysts may be prepared by techniques well known in the art. For example, such preparation may include coprecipitation or impregnation techniques. One can employ extrudates or pellets for impregnation of powders followed by pelletization or extrusion to yield the finished catalyst. When employing impregnation techniques, the metals may be added to the base singly or in combination, utilizing water soluble salts such as borates, boric acid, halides, nitrates, sulfates, acetates, etc. Easily hydrolyzed salts can be kept in solution without decomposition by employing the appropriate inorganic acids. Well-known procedures for drying and calcination of the catalyst will also be employed. For example, vacuum drying at a temperature of about 250 F. and calcination in an oxidative, neutral or reductive atmosphere, utilizing a calcination temperature of about 800 to 1200 F. can be practiced.
The following Table I illustrates the advantages of a tin-boria-alumina catalyst as compared with boria-alurnina alone for the disproportionation of toluene at 948 F., 800 p.s.i.g., a liquid hourly space velocity of 0.44 and a hydrogen-to-hydrocarbon ratio of 3/ 1.
TABLE I 10% BzOaSnO Catalyst 10% B203/A1203 (2%)lA12O3 Con. of toluene (wt. percent liq.
prod. 41. 0 40. 9 Recovery (vol. percent) 95. 4 95. 1 Time on stream (hr.) 2. 5 6. 0 Rate of deactivation (A wt -2. 3 0 2. 3 4. 8 20. 2 23. 0 58. 6 59. 1 18. 9 9. 9 Xylene 0. 0 3. 2
Three additional 6 hour runs were made with the same SnO promoted catalyst (not regenerated) at varying severities with no apparent deactivation.
In accordance with the present invention, an integrated process for the production of benzene and para-xylene from toluene can be carried outwith resultant high yields of these two valuable products. This process is best described by reference to the drawing.
In accordance with the drawing, toluene is introduced to the system through line 10, hydrogen is added through line 12 and these materials are passed over the catalyst of the present invention in the disproportionation reactor 14. The efiluent passing through line 16 is passed to a flash drum for the removal of hydrogen and any light gases produced. These materials are discharged through line 18. Since little or no demethanation occurs, the hydrogen is substantially pure and may be recycled to the disproportionation reaction without further treatment. However, in some instances, further purification of the hydrogen is necessary before recycle or reuse. The liquid product passes through line 20 to a first distillation unit 22. In distillation unit 22, benzene is recovered as an overhead through line 24. The bottoms product from distillation unit 22 passes through line 26 to a second distillation unit 28. In distillation unit 28, toluene is removed as an overhead product and recycled to the disproportionation section through line 30. The bottoms product from distillation unit 28 is a mixture of xylenes which is discharged through line 32. This product may be withdrawn, as such, through line 34. Preferably, however, the xylene product is passed through line 36 to crystallization unit 38. In crystallization unit 38, para-xylene is selectively removed and withdrawn through line 40. The mother liquor from the crystallization section is passed through line 42 to an isomerization unit 44. Hydrogen is added through line 46. In the isomerization unit 44, the equilibrium concentration of para-xylene is re-established and the material may then be recycled through line 48 to crystallization unit 38 for further para-xylene separation.
The isomerization reaction should be carried out under more mild conditions than the disproportionation. Catalysts useful in the disproportionation reaction might also be used in the isomerization or conventional catalysts, such as platinum on silica-alumina, can be used. The isomerization may be carried out at temperatures of about 500 to 900 F., and preferably 550 to 650 F., pressures of 50 to 2000 p.s.i.g., and preferably 300 to 600 p.s.i.g., at a liquid hourly space velocity of 0.1 to 10, and utilizing a hydrogen-to-hydrocar-bon mole ratio between about 1 and 20 to l.
The present invention is further exemplified by the following Table II.
Table IV shows the results of using stoichiometric or greater amounts of a metal salt with boric acid to prepare the catalyst, thereby producing a metal borate. Accordingly, less than stoichiometric amounts of the metal should be used with the boria.
Feed Toluene Toluene Conditions:
Temp., F 1, 000 1,000 Pressure, p.s.l.g. 800 800 LHSV 0.5 0.5 Ha/HO 3/1 3/1 Recovery, vol. percent 87 87 Toluene conversion 15 17 Product distribution- 0.2 0.3 2. 7 5. 0 Toluene. 97. 0 94. 2 Xylene. 0. 2 Xylene Carbon on catalyst, wt.
percent feed 0.38 0. 31
When reference is made herein to the Periodic System of Elements, the particular groupings referred to are as set forth in the Periodic Chart of the Elements in The Merck Index, Seventh Edition, Merck & Co., Inc., 1960.
The term alkyl transfer of alkyl aromatics as used herein is meant to include disproportionation and transalkylation. Disproportionation, in turn, is meant to include conversion of two moles of a single aromatic, such as toluene, to one mole each of two different aromatics, such as xylenes and benzene. Transalkylation is meant to include conversion of one mole each of two different aromatics, such as xylenes and benzene, to one mole of a single different aromatic such as toluene. The alkyl trans- TABLE II 10% 13203 11102 10% B203-K2O 10% BzOs-CaO V 10% 13203-080 Cata yst (2%)/A120a (2%)/A120a (2%)]Ah0a (2%) /A12O3 Feed Toluene Toluene Toluene Toluene Conditions.
Temp., 950 950 1, 000 950 Pressure, p s 1 g. 800 800 80 800 0. 5 0. 5 1 0. 5 Ila/hydrocarbon 3 3 3 3 Analysis, G.C., wt. percent q. prod.:
Benzene 19. 6 8. 5 2. 3 4. 1 Benzene- 15. 9 3. O 6. 0 6. 7 Toluene- 50. 1 87. 8 88. 7 84. 2 Xylene- 13. 0 0. 6 3. 0 4. 6 Xylene 1. 4 0. 1 0. 4 Conversion of toluene 49. 9 12. 2 11. 3 15. 8
Table III below shows the use of a catalyst, made in accordance with the present invention, to disproportionate xylene.
fer defined above is also to be distinguished from isomerization where there is no transfer of alkyl groups from one molecule to another 'but simply a shifting of alkyl groups around the aromatic ring, such as isomerization of xylenes, or rupture of the ring or the alkyl side chain and rearrangement of split-off carbon atoms on the same molecule. The alkyl transfer is also to be distinguished from a hydrogen transfer reaction, such as the hydrogenation of aromatics, the dehydrogenation of cycloparaffins and like reactions.
We claim:
1. A process for the alkyl transfer of alkyl aromatics; comprising, contacting an alkyl aromatic feed material with a catalyst consisting essentially of about 1 to 15% by weight of a metal of Groups I-A, II-A, IV and rare earth metals of the Periodic System and mixtures thereof and about 5 to 25% by weight of boria deposited on an alumina base, under conditions sufiicient to cause disproportionation of said alkyl aromatics.
2. A process in accordance with claim 1 wherein the metal is a metal of Group I-A.
3. A process in accordance with claim 1 wherein the metal is a metal of Group II-A.
4. A process in accordance with claim 1 wherein the metal is a metal of Group IV.
5. A process in accordance with claim 1 wherein the metal is a rare earth metal.
6. A process in accordance with claim 1 wherein the metal is a mixture of Group IV and a metal selected from the group consisting of Groups I-A, II-A and rare earth metals. 1
7. A process in accordance with claim 1 wherein the feed material contains substantial volumes of toluene.
8. A process in accordance with claim 7 wherein unconverted toluene is separated from the alkyl transfer product and said unconverted toluene is recycled to the disproportionation step.
9. A process in accordance with claim 7 wherein xylenes are separated from the alkyl transfer product and paraxylene is separated from said xylenes.
10. A process in accordance with claim 8 wherein the xylenes remaining after the separation of para-xylene are subjected to isomerization conditions sufiicient to produce additional para-xylene.
11. A process in accordance with claim 1 wherein the flow of feed material through the catalyst is interrupted periodically and the flow of hydrogen is continued for a time sufficient to reactivate the catalyst.
12. A process in accordance 'with claim 1 wherein the flow of feed material and hydrogen through the catalyst is discontinued and the catalyst is calcined in air under conditions suflicient to reactivate the catalyst.
References Cited UNITED STATES PATENTS 2,795,629 6/1'957 Boedeker 260668 3,079,447' 12/1963' Bartlett et al 260668 3,113,979 12/19 63 Bartlett et al. 260668 3,211,798 10/1965 Burk et a1 260-668 3,233,002 12/1966 Kovach et al. 260672 3,350,469 1967 Ryan 260-672 DELBERT E. GANTZ, Primary Examiner G. E. SCHMITKONS, Assistant Examiner US. Cl. X.R.
252-432, 462, 463; 260668A, 672T, 674A
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78523268A | 1968-12-19 | 1968-12-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3598879A true US3598879A (en) | 1971-08-10 |
Family
ID=25134835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US785232A Expired - Lifetime US3598879A (en) | 1968-12-19 | 1968-12-19 | Alkyl transfer of alkyl aromatics with group i-a,ii-a,iv,or rare earth metals on boria alumina |
Country Status (1)
Country | Link |
---|---|
US (1) | US3598879A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3849261A (en) * | 1971-02-26 | 1974-11-19 | Anvar | Method for separating hydrocarbons especially aromatic hydrocarbons and installations therefor |
US3883442A (en) * | 1972-05-19 | 1975-05-13 | Union Oil Co | Non-shrinking alumina-based catalyst compositions |
US4007231A (en) * | 1975-11-24 | 1977-02-08 | Mobil Oil Corporation | Selective production of para-xylene |
US4115424A (en) * | 1976-12-22 | 1978-09-19 | Monsanto Company | Zeolite catalyst |
US4219690A (en) * | 1979-07-05 | 1980-08-26 | Ashland Oil, Inc. | Alkylation of aromatics with olefins in the presence of an alumina catalyst |
US4285835A (en) * | 1979-07-05 | 1981-08-25 | Ashland Oil, Inc. | Catalyst for alkylating aromatics with olefins |
US4851604A (en) * | 1987-09-02 | 1989-07-25 | Mobil Oil Corp. | Toluene disproportionation |
US4962257A (en) * | 1988-10-06 | 1990-10-09 | Mobil Oil Corp. | Process for the catalytic disproportionation of toluene |
US5030787A (en) * | 1990-01-24 | 1991-07-09 | Mobil Oil Corp. | Catalytic disproportionation/transalkylation utilizing a C9+ aromatics feed |
EP0641253A4 (en) * | 1991-06-20 | 1994-06-01 | Catalytica Inc | A method for regenerating lewis acid-promoted transition alumina catalysts used for isoparaffin alkylation by calcination. |
US5329059A (en) * | 1993-07-06 | 1994-07-12 | Mobil Oil Corp. | Alkylaromatic disproportionation |
US5488194A (en) * | 1994-05-16 | 1996-01-30 | Mobil Oil Corp. | Selective production of para-dialkyl substituted benzenes and catalyst therefor |
US5569805A (en) * | 1993-10-18 | 1996-10-29 | Mobil Oil Corporation | Catalytic conversion of aromatic compounds |
-
1968
- 1968-12-19 US US785232A patent/US3598879A/en not_active Expired - Lifetime
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3849261A (en) * | 1971-02-26 | 1974-11-19 | Anvar | Method for separating hydrocarbons especially aromatic hydrocarbons and installations therefor |
US3883442A (en) * | 1972-05-19 | 1975-05-13 | Union Oil Co | Non-shrinking alumina-based catalyst compositions |
US4007231A (en) * | 1975-11-24 | 1977-02-08 | Mobil Oil Corporation | Selective production of para-xylene |
US4115424A (en) * | 1976-12-22 | 1978-09-19 | Monsanto Company | Zeolite catalyst |
US4219690A (en) * | 1979-07-05 | 1980-08-26 | Ashland Oil, Inc. | Alkylation of aromatics with olefins in the presence of an alumina catalyst |
US4285835A (en) * | 1979-07-05 | 1981-08-25 | Ashland Oil, Inc. | Catalyst for alkylating aromatics with olefins |
US4851604A (en) * | 1987-09-02 | 1989-07-25 | Mobil Oil Corp. | Toluene disproportionation |
US4962257A (en) * | 1988-10-06 | 1990-10-09 | Mobil Oil Corp. | Process for the catalytic disproportionation of toluene |
US5030787A (en) * | 1990-01-24 | 1991-07-09 | Mobil Oil Corp. | Catalytic disproportionation/transalkylation utilizing a C9+ aromatics feed |
EP0641253A4 (en) * | 1991-06-20 | 1994-06-01 | Catalytica Inc | A method for regenerating lewis acid-promoted transition alumina catalysts used for isoparaffin alkylation by calcination. |
EP0641253A1 (en) * | 1991-06-20 | 1995-03-08 | Catalytica Inc. | A method for regenerating lewis acid-promoted transition alumina catalysts used for isoparaffin alkylation by calcination |
US5329059A (en) * | 1993-07-06 | 1994-07-12 | Mobil Oil Corp. | Alkylaromatic disproportionation |
US5569805A (en) * | 1993-10-18 | 1996-10-29 | Mobil Oil Corporation | Catalytic conversion of aromatic compounds |
US5488194A (en) * | 1994-05-16 | 1996-01-30 | Mobil Oil Corp. | Selective production of para-dialkyl substituted benzenes and catalyst therefor |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3686340A (en) | Hydrodealkylation process | |
US2734929A (en) | Dealkylation of hydrocarbons | |
US3598879A (en) | Alkyl transfer of alkyl aromatics with group i-a,ii-a,iv,or rare earth metals on boria alumina | |
US2960545A (en) | Demethylation process for pseudocumene | |
US3607961A (en) | Alkyl transfer of alkyl aromatics with group viii metals on boria-alumina | |
US3551509A (en) | Moving bed process using sieve catalyst to make xylenes by toluene disproportionation and transalkylation with c9-c10 alkylbenzenes | |
US3679773A (en) | Dehydrogenation-type reactions with group viii catalysts | |
US3699181A (en) | Alkyl transfer of alkyl aromatics with group vib metals on mordenite | |
KR100338424B1 (en) | Process for preparing 2,6-dialkylnaphthalene | |
US3291850A (en) | Hydrodealkylation of alkyl aromatic hydrocarbons | |
US4202996A (en) | Hydrocarbon isomerization process | |
US3598878A (en) | Alkyl transfer of alkyl aromatics with vanadium on zeolites | |
US3078318A (en) | Production of specific xylene isomers | |
US4538017A (en) | Conversion of paraffins to aromatics | |
US3919339A (en) | Hydrogenolysis/isomerization process | |
US3211798A (en) | Method for transalkylation and isomerization of methyl benzenes | |
US3825503A (en) | Hydrogen transfer catalyst | |
US4524230A (en) | Preparation of alkylaromatic compounds | |
US3597491A (en) | Alkyl transfer of alkyl aromatics with croup vi-b metals on type y zeolites | |
US3374281A (en) | Production of alkylated benzenes from paraffins | |
US3691247A (en) | Selectively removing monoalkylbenzenes from mixtures thereof with dialkylbenzenes | |
US3548017A (en) | Xylene isomerization process | |
US2848514A (en) | Process for producing diisopropyl benzenes | |
US4041089A (en) | Process for the isomerization of dimethylnaphthalenes using a mordenite/alumina catalyst | |
US3879484A (en) | Hydrocarbon isomerization process |